Process of treating hydrocarbon oil with metallic halides



Aug. 25, 1.931. R. w. HANNA vPROCES'S 0F TREATING HYDROCARBON OILS WITH METALLIC HALIDES Filed Nov.

Sal Wt klit Patented Aaggzzs, 1931 f UNITED" sfr-Aras PATENT OFFICE RICHARD w. Bunn, or rrEnMoNr,

CALIFORNIA, ASSIGN OR T STANDARD OILCOM- PAN Y OF CALIFORNIA, IFItAIl'CISt'O, CALIFORNIA, A CORPORATION OF DELA.

WARE 1 rRooEss OF'TREATING nYDRooABBoN o IL WITH METALLIC :Miramas Application mea November 27, 192e..` serial No. 151,164.

a metallic halide such, for example, as alumi- ,5` num chloride for ferrie chloride'.` The proc` ess is employed either for the production of higherboiling point oils fromilower boiling point oils, or for lower boiling. point oils from higher boiling point oils, or for the purpose of producing saturated and unsaturated or ring structure hydrocarbons-from unsaturated hydrocarbons. In the customary processes of treating hydrocarbon oil with `a metallicv halide, the lmetallic halide is all added to the hydrocarbon oil at the' start of the4 treatment. With such .a process,all of the tar or aluminum chloride sludge formed becomes` admixed with the aluminum chloride', Substantially decreasing the eiciencyvof the reac'- tion.

An object of thepresentinvention is to provide a process for treating' hydrocarbon oils with a metallic halide kby which the .25 metallic halide can beeconomically applied to the hydrocarbon oil in a plurality "of steps with anintermediate removal or separation from the hydrocarbon oils of the tar or sludge produced in each step.

By the process of the' present invention, freshmetallic-chloride is not diluted by the sludge or tar from the spent aluminum chloride so that said metallic halide'is in superior -^condition for efficient conversion of the hy'- 35 drocarbon oil. Moreover,

by the process of the present invention, the metallic halide applied to the hydrocarbon voilin the first step may be caused to remove substantially all of the oxygen or oxygen compounds from 40 the' hydrocarbon oil. whereby all.. metallic halide added in the subsequent treating step or steps Will be contacted with anfoxygen- -free oil and, moreover, will not come into contact with any products of reaction tween metallic halide and oxygen. The 1 process of the present invention thus produces a metallic halide residue in ,the sec- .i ond and in following steps in the treatment, which is free of oxygen compounds and can 5,0 be mere-.readily processedA for recovery or' the ent invention, the hydrocarbon oil and rst portion of metallic halide are first contacted together at a reaction temperature and pref- .cally and partially in vertical section.

aluminum chloride content.` Furthermore, by the process ofthe present invention, the hydrocarbon oil in the last stages. of its treatment is brought into contact with fresh uncontaminated metallichalide with the result that a more complete conversion ofthe hydrocarbon oil by the` metallic halide may be obtained.

f In accordance with the process of the preserably'under a pressure suiicient to maintain all of the admixture in a substantially'liruid phase. After said first portion. of meta lic halide has Abeen caused to exert its full treating effect upon the hydrocarbon oil and remove allof the oxygen compounds therefrom, said admixture is passedA into a dis v tillatory chamberwhereitspressureis dropped preferably below atmospheric to separate therefrom the oil content from the.. metallic halide residue under the residual heat of the admixture' either with orwithout additional heating. The vapors are then fractionally condensed to separate therefrom the converted from unconverted Ioil and the unconverted oilis then accumulated or continuously passed yfor treatment with the second portion lof metallic halide into the same' reaction chamber or through another reaction' blhamber lwhile said unconverted oil is still A The process of the present invention, together with various additionalobjects. and advantages derived therefrom will be understood rom a description of a referred form' or example of a process embo ying the present invention.. For this purpose, the preferred process will be described as it is carried out in connection with an apparatus illustrated v in the accompanying drawing.

In the drawing: A The apparatus is indicated diagrammati- Referring to the drawing, the fresh oil to the system is taken from a 'source (not shown) by pump 2 and forced through line 3 to a heating coilfland'enters into a reaction chamber 5. The line 3 may pass 100 through one or more heat exchangers or planers for the various dephlegmators of the system, and is indicated as preferably leading through the planers 6 and 7 of the dephlegmators 8 and 9.

The heating coil 4 is indicated as mounted within suitable heating means 10, such as the furnace having a burner 11. The reaction chamber 5 may also be mounted over a suitable heating means, such as a burner 12,

o `sure regulating valve 18 and hence into a flash or distillatory chamber 19. The flash or distillatory chamber 19 may, if desired, be mounted over suitable heating means, such as a furnace having a bulrner20. The flash chamber 19 preferably is provided with a residual draw off line 21,provided with a pump 22. The flash chamber 19 is also provided with a vapor line 23 leading to the de'phlegmator 9.

The dephlegmator 9 is connected with a vapor line 24 which leads to a condenser 25 and hence to a receiver 26, which receiver may be maintained under vacuum or reduced pressure by a vacuum pump 27. The dephlegmator 9 is also preferably provided with a condensate line 28 which connects with line 29 provided with a pump 30. The pump 30 may lead to any suitable place for accumula-ting the condensate for further treatment but preferably passes the condensate directly continuously into a second reaction chamber 31, which may be similar to reac- .tion chamber 5. The reaction chamber 31 is provided with an aluminum chloride `charger 32 and also may be mounted over a furnace 33. The reaction chamber 31 has a draw-off line 34 leading through a pressure regulating valve 35 and hence to a flash or distillatory chamber 36, which distillatory chamber may be mounted over a furnace 37 The distillatory chamber 36 may have a residual line 38 provided with a pump 39 and a vapor line 40.

The vapor line 40 leads to a dephlegmator 8, which dephlegmator 8 is provided with a lvapor line 41 which may lead to the condenser 25. The dephlegmator 8 is also providedwith a condensate line 42 which may lead' to any place for accumulating 1the condensate for further treatment but preferably leads to the line 29, by which it is recirculated back into reaction chamber 31.

With the apparatus thus described, the preferred process is as follows: The hydrocarbon oil to be treated may be any hydro- 300 to 70()o F. The metallic halide, such as aluminum chloride, is continuously or intermittently added t0 the hydrocarbon oil in reaction chamber 5. The quantity of metallic halide employed will also vary but an example of a suitable quantity to employ is from .O5 to .2 pounds of metallic halide per gallon of oil treated in reaction chamber 5. Said metallic halide is less than sufiicient l:to cause complete conversion of the hydrocarbon oil fed into the reaction chamber 5 but is admixed therewith until its ability to react upon the hydrocarbon oil is substantially completely exhausted. The reaction isconsiderably facilitated by maintaining all of the admixture and products of. rcaction in liquid state and, accordingly, the admixture in reaction chamber 5 is held under a pressure suliciently above atmospheric to maintain the materials substantially all in liquid state` The admixture from reaction chamber 5 is withdrawn preferably continuously and. passed through the pressure regulating Valvey wherein the pressure of the admixture is permitted to drop. The admixture passes into flash or distillatory chamber 19 wherein the hydrocarbon oil is vaporized through the residual heat therein or under the additional aid of heat from burner 20 so that all of the hydrocarbon oil is separated from the spent metallic halidel residue. Preferably and usually the metallic halide residue will thereby be reduced to solid material or coke.

'In certain cases, however, a liquid metallic halide residue is produced, in which case the same may be continuously withdrawn from line 21 by pump 22.

This initial or rst reaction between th metallic halide and hydrocarbon oil results in substantial elimination of oxygen or oxygen-bearing compounds from the hydrocarbon oil with the result that the hydrocarbon oil is now substantially free of oxygen compound, all of said oxygen and oxygen compounds being left in the coke or residue in the distillatory chamber 19. The hydrocarbon vapors are preferably fractionated in dephlegmator 9 so that the produced light vapors or naphtha remain as vapors passing from dephlegmator 9 through line 24 and being condensed in condenser 25, while all of the heavier or higher boiling point vapors are condensed in dephlegmator 9, from which they may be withdrawn through line 26. Preferably, both the flash chamber 19 and the fractionatmg apparatus are maintained under a reduced f ressure such, for

example, as 2 to 5 poun s per square inch The heavy hydrocarbon oil in line 26 may be passed to a suitable placefor accumulating the same, after which the said hydrocarbon oil may be passed back to reaction chamber 5 for contact with further metallic halide but preferably said hydrocarbon oilis passed immediately and continuously into the second reaction chamber 31 and therein immediately contacted with further metallic halide. The amount of metallic halide added in the second reaction chamber 31 may be sufficient to complete the conversion treatment, or only a portion of the metallic halide necessary to complete the conversion treatment may be added, in which case the unconverted oil may be againcontacted with one or more following portions of metallic halide. Preferably, -however, sufiicient metallic halide is added in the second reaction chamber 31 to complete the treatment.

For example, when employing a familiar gas oil fraction of a California base crude petroleum oil, I add to the hydrocarbonoil in the second reaction chamber 31 approximately .2 to .8 pounds of metallic halide per gallon of oil processed. Said metallichalide preferably is either continuously or intermittently added to reaction chamber 31. The metallic halide and hydrocarbon oil in reaction chamber 31 is continuously agitated together at a reaction temperature. The reaction temperature `is preferably maintained by supplying. heat from burner 33,y although it is understood that the hydrocarbon oil may, if desired, be preheated in line 29 to the reaction'temperature before it is introduced into the reaction chamber 31. In this case, no heat need be supf plied to reaction chamber 31. The admixture in reaction chamber 31 is also preferably maintained under a pressure above atmospheric 'so that the produced low boiling point oils are maintained "liquid, thereby preventing lconcentration of the admixture in metallic halide residue. The admixture is continuously withdrawn in liquid state from the reaction chamber 31 and therefrom preferably passed through a pressure regu-I.

-lating or releasing valve 35 into the iash or distillatory chamber 36. This chamber is likewise preferabl maintained under the vacuum or reduce pressure from pump 27 and Within said chamber, all of the hydrocarbon oilv is vaporized from the metallic halide residue. This vaporization may, Y.

at times, be accomplished solely through the residual heat in the admixture and at other times, additional heat may be necessary, in which case it is supplied from burner 37.

In flash chamber 36, themetallic halide resf' idue is usually reduced solid material or coke. In certain cases, however, a liquid material will be produced, in which case it is withdrawn through line 38 by pump 39.

All of the hydrocarbon oil as vaporize is passed -to dephlegmator 8 wherein tlie vvapors are fractionated to condense therefrom all ofthe highboiling point .or unconvertedoil while the low boiling point oil or naphtha produced is dischargedfrom the dephlegmator through line 41 and passed through condenser 25 to the receiver v26. The high boiling point oil is withdrawn from dephlegmator '8 and passes through line 42 to a place for further treatment,

preferably being p recirculated along with the oil continuously passing from line 26 back into reaction chamber 31 for further contact with metallic halide. l

' All of the metallic halide residue obtainedy in iiash or distillatory chamber 36 is substantially free of oxygen or oxygen containing compounds' and 'thereafter is in condition to be readily processed for recover of its metallic halide component. Inasmuc as under the preferred recess, the' greater portion of metallic ha ide is collected as spent metallic halide in the distillatory or flash chamber `36, the greater portion of metallic halide employed in the processis converted into a form .from whichthe metallic ously diverted from the system part of the heavy oil, for example, bycontinuously passing all or part of the oil from line 42 out of the system, after which said oil may be processed for the manufacture of high grade lubricating oils.

jectsof the invention, it is understood that numerous modifications may be made with- 'outy departing fromthe principles of the' invention and the invention includes all such changes, modifications, and substitution of equivalents as come'within .the scope of the following claims.

I claim:

desired to( While the process particularly described I herein is well adapted to carry out the ob- 1. A process of treating hydrocarbon oil --with metallic halide, which comprises heating the hydrocarbon oil to a vtemperature sufficient to decompose the hydrocarbon oil into lower boiling point oil when contacted with metallic halide, then contacting the heated hydrocarbon oil with anhydrous metallic halide at such temperature and undern a pressure sufficient to maintain the same in substantially liquid phase, then passing said adi'nixture into a chamber maintained under substantially reduced pressure, therein vaporizing hydrocarbon oil to separate it from residue retaining substantially all the metallic halide in the spent condition, fractionating from said vapors unconverted hydrocarbon oil, and then again contacting said unconverted hydrocarbon oil, at a temperature sufficient for decomposing the oil into lwer boiling point oil, with metallic halide under a pressure sufficient to maintain the hydrocarbon oil in substantially liquid phase in a decomposing zone, separate from the zone in which the fresh hydrocarbon oil is decomposed.

2. A process of treating hydrocarbon oil with metallic halide, which comprises heating the hydrocarbon oil to a temperature sufficient to decompose the oil when admixed with metallic halide, then contacting the heated hydrocarbon oil with metallic halide at such temperature and under a pressure suiicient to maintain the same in -substair tially liquid phase, passing the admixture into a chamber, maintaining said chamber under a substantially reduced pressure, vaporizing hydrocarbon oil from the coke in which substantially all of the metallic halide is retained inthe spent condition, fractionating the unconverted hydrocarbon oil from the produced lower boiling point oil, and again contacting said unconverted hydrocarbon oil with further metallic halide under a temperature suflicient to convert said hydrocarbon oil into lower boiling point oil and under a pressure sufficient to maintain the same in substantially liquid phase, and in a reaction zone maintained separate from the reaction zone in which the fresh hydrocarbon oil is decomposed.

A process of continuously treating hydrocarbon oil with anhydrous metallic halide which comprises, continuously heating the hydrocarbon oil to a temperature sufiicient to decompose the oil when admixed with metallic halide, and then continuously contacting the heated hydrocarbon oil and metallic halide together at suchtempcrature and under a pressure sufiicient to maintain the said admixture substantially in liquid phase, the ratio of metallic halide to oil being maintained at a ratio,less than that sufficient to effect complete conversion, passing the admixture to a vaporizing Zone maintained under substantially lower pressure, therein continuously vaporizing hydrocarbon oil to separate it from residue retaining substantially all the metallic halide in the spent condition, continuously fractionating from said vapors the unconverted hydrocarbon oil, and continuously contacting said unconverted hydrocarbon oil with a further portion of metallic halide under pressure sufiicient to maintain the admixture substantially in liquid phase and at a tem perature sufiicient to decompose the oil into lower boiling point oil, and in a separate zone from the decomposing Zone in which the first decomposing action is carried out.

4. A process of treating hydrocarbon oil with anhydrous metallic halide which comprises, heating the hydrocarbon oil to a temperature sufficient to decompose the hydrocarbon oil into lower boiling point oil when contacted with metallic halide and then contacting the hydrocarbon oil with metallic halide in a first decomposing Zone under a pressure sufficient to maintain the admiX- ture in liquid state until the metallic halide is substantially spent, thereafter reducing the pressure whereby hydrocarbon oil is vaporized 'from the spent metallic halide residue, fractionating from said vapors the unconverted oil, and again contacting said unconverted oil in a second decomposing zone with a further portion of metallic halide and under a pressure sufficient to maintain the hydrocarbon oil in liquid state and at a temperature sufiicient to decompose hydrocarbon oil into lower boiling point o1 5. A process of treating hydrocarbon oil with anhydrous metallic halide which comprises, heating the hydrocarbon oil in a coil to a temperature sufficient to effect the decomposing reaction on the oil when admixed with metallic halide, continuously contacting the hydrocarbon oil in a first reaction zone with a portion only of the metallic halide necessary to secure complete reaction and under a pressure sufficient to keep the admixture in liquid phase for a prolonged period of contact, continuously cleansing the hydrocarbon oil from the spent metallic halide by passing the adlnixture into a flashing Zone maintained under a reduced pressure, continuously fractionating the unconverted hydrocarbon oils from the pro duced lower boiling ,point oils, and continuously contacting said unconverted hydrocarbon oils with a further portion of metallic halide in the second separate decomposing Zone and under a pressure sufficient to keep the admixture in liquid phase and ata temperature sufiicient to vdecompose the oils into lower boiling point oils.

Signed at San Francisco, California, this 16th day of November, 1926.

RICHARD W. HANNA. 

